Preparation of poly(octatriazacane)

ABSTRACT

A polyoctatriazacane molecule is disclosed that has a plurality of octatriazacane groups having the structure 
                         
and a plurality of divalent bridging groups, each divalent bridging group comprising an aromatic group.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. patent applicationSer. No. 14/305,648, filed Jun. 16, 2014. The aforementioned relatedpatent application is herein incorporated by reference in its entirety.

BACKGROUND

The present disclosure relates to methods of making poly(octatriazacane)materials.

New polymer-forming reactions are difficult to design due to strictrequirements for efficient, straight-forward, and clean chemistry. Smallmolecule octatriazacanes have been synthesized previously but have neverbeen explored as a potential polymer-forming reaction. A new and simplepolymer forming polycondensation of diamines with paraformaldehyde topoly(hexahydrotriazine)s and poly(hemiaminal)s has been previouslydescribed.

These poly(hexahydrotriazine)s exhibited high Young's modulus (˜14.0 GPafor the freestanding films) but are completely amorphous and generallylack free volume within their polymer matrix due to their high crosslinkdensity. Additionally, these polymers suffer from poor yield strengthand solubility and electron-deficient monomers do not react to formpolymer according to this reaction scheme. Therefore, polymers that arestructurally similar to the poly(hexahydrotriazine)s andpoly(hemiaminal)s but having improved yield strength and solubility andwhich might incorporate electron-deficient monomers would be ofinterest.

A need exists for methods of making new polymers having improvedproperties and better performance in the areas described above.

SUMMARY

According to one embodiment, a polyoctatriazacane is a molecule having aplurality of octatriazacane groups having the structure

and a plurality of divalent bridging groups, each divalent bridginggroup comprising an aromatic group. Each divalent bridging group mayhave the general structure

wherein R¹, R², R³, and R⁴ are each, individually, H, Cl, CN, F, NO₂,SO₃, heterocycles such as imides, benzoxazoles, benzimidazoles,phenylquinoxalines, C_(x)H_(2x+1-y)R⁵ _(y), or C₆H_(5-a)R⁵ _(a), whereinR⁵ is Cl, F, SO₃, C₆H_(5-a)R⁶ _(a), or NH_(3-b)R⁶ _(b), wherein R⁶ isC_(x)H_(2x+1), C_(x)H_(2x), or C₆H₅, where in each instance x is aninteger from 1 to 4, y is an integer from 0 to 2x+1, a is an integerfrom 0 to 5, and b is an integer from 0 to 3; or the general structure

wherein L′ is a divalent linking group selected from the groupconsisting of *—SO₂—*, *—N(R′)—*, *—N(H)—*, *—CF₂—*, *—C(CF₃)₂—*,*—R″—*, and combinations thereof, wherein R′ and R″ independentlycomprise at least 1 carbon.

According to another embodiment, a method of forming apolyoctatriazacane may include forming a reaction mixture comprising ai) solvent, ii) a formaldehyde, and iii) a monomer comprising twoprimary aromatic amine groups; and forming a polyoctatriazacane byadding formic acid to the reaction mixture. In one embodiment,p-phenylenedianiline is reacted with paraformaldehyde and formic acid inDMSO to produce poly-N,N,N-(p-phenylenedianiline)-octatriazacane.

The above-described embodiments and other features and advantages of thepresent disclosure will be appreciated and understood by those skilledin the art from the following detailed description, drawings, andappended claims.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a ¹H-NMR analysis of a polyoctatriazacane according to oneembodiment.

DETAILED DESCRIPTION

Methods of making polyoctatriazacanes are described. Polyoctatriazacaneshave the general structure

A plurality of trivalent octatriazacane groups are bonded, at thestarred bonds, to divalent linking groups having the general structure*—K′—*, where K′ comprises an aromatic group. A polyoctatriazacaneaccording to formula (1) may be made by mixing together a diamine, or amixture of diamines, having the general structure H₂N—K′—NH₂, where K′is defined as above, with an aldehyde (i.e. formaldehyde,paraformaldehyde, acetaldehyde, benzaldehyde, etc.), a solvent, andformic acid.

K′ may be a substituted or unsubstituted phenylene group having thegeneral structure of formula (2):

where R¹, R², R³, and R⁴ are each, individually, H, Cl, CN, F, NO₂, SO₃,heterocycles such as imides, benzoxazoles, benzimidazoles, andphenylquinoxalines, C_(x)H_(2x+1-y)R⁵ _(y), or C₆H_(5-a)R⁵ _(a), whereR⁵ is Cl, F, SO₃, C₆H_(5-a)R⁶ _(a), or NH_(3-b)R⁶ _(b), where R⁶ isC_(x)H_(2x+1), C_(x)H_(2x), or C₆H₅, where in each instance x is aninteger from 1 to 4, y is an integer from 0 to 2x+1, a is an integerfrom 0 to 5, and b is an integer from 0 to 3. Thus, in addition to anaromatic group, K′ may have fluorine, chlorine, or sulfonate groups.Exemplary diamine reactants of this type include phenylene diamine, afluoromethyl phenylene diamine such as a phenylene diamine in the paraor meta configuration with one to four fluoromethyl groups, each ofwhich may have one to three fluorine atoms, an alkyl fluoromethylphenylene diamine with a mixture of alkyl and fluoromethyl substituents,or a phenylene triamine with no more than one amino group havingsubstituents, may also be used. For example,tetrakis-(2,3,5,6-trifluoromethyl)-1,4-diamino benzene,bis-(2,5-trifluoromethyl)-1,4-diamino benzene, or2-fluoromethyl-bis-(3,5-difluoromethyl)-1,4,-diamino benzene may beused.

K′ may also be a polynuclear aromatic group, such as a naphthalenegroup, an acenaphthene group, an acenaphthylene group, a fluorene group,a phenalene group, or an anthracene group, any of which may besubstituted at any non-amino carbon atom with substituted orunsubstituted alkyl or aryl groups or halogens, or may be partiallysaturated (e.g. dialin, tetralin groups). K′ may also be a substitutedor unsubstituted indene, indane, or indole group.

K′ may also be a phenyl containing group having the general structure offormula (3)

where R⁷ is a substituted or unsubstituted alkyl, aryl, or polyaromaticgroup, any of which may be substituted at any non-amino carbon atom witha substituted or unsubstituted alkyl or aryl group, or a halogen. Thus,R⁷ may be SO₂, C_(x)H_(2x-y)R⁵ _(y), or C₆H_(5-a)R⁵ _(a), with x, y, anda defined as above.

K′ may also be a diphenyl group having the formula (4):

wherein L′ is a divalent linking group selected from the groupconsisting of *—SO₂—*, *—N(R′)—*, *—N(H)—*, *—CF₂—*, *—C(CF₃)₂—*,*—R″—*, and combinations thereof, wherein R′ and R″ independentlycomprise at least 1 carbon. In an embodiment, R′ and R″ areindependently selected from the group consisting of methyl, ethyl,propyl, isopropyl, phenyl, and combinations thereof. For example, L′ maybe a linear hydrocarbyl group having from 1 to 4 carbon atoms. Other L′groups include methylene(*—CH₂—*), isopropylidenyl(*—C(Me)₂-*), andfluorenylidenyl:

A phenylenedianiline such as p-phenylenedianiline may be used as adiamine reactant. A polyoctatriazacane may have a mixture of linkinggroups of formula (1) and formula (2).

In an embodiment, a polyoctatriazacane is a crosslinked polymercomprising i) a plurality of trivalent octatriazacane groups of formula(1) covalently linked to ii) a plurality of divalent bridging groups K′according to the descriptions of K′ above. Each starred bond of a givenoctatriazacane group of formula (1) is covalently linked to a respectiveone of the bridging groups K′. Additionally, each starred bond of agiven bridging group K′ is covalently linked to a respective one of theoctatriazacane groups.

Exemplary non-limiting divalent bridging groups include:

and combinations thereof

The polyoctatriazacanes described herein can further comprise monovalentaromatic groups (referred to herein as diluent groups), which do notparticipate in chemical crosslinking and therefore can serve to controlthe crosslink density as well as the physical and mechanical propertiesof the polyoctatriazacane polymers. Monovalent diluent groups have astructure according to formula (5), formula (6), formula (7), and/orformula (8):

wherein W′ is a monovalent radical selected from the group consisting of*—N(R¹)(R²), *—CF₂—*, *C(CF₃)₂—*, *—OR³, —SR⁴, wherein R¹, R², R³, andR⁴ are independent monovalent radicals comprising at least 1 carbon. Thestarred bond is linked to a nitrogen of an octatriazacane group.

Non-limiting exemplary diluent groups include:

wherein the starred bond is linked to a nitrogen of an octatriazacanegroup. Diluent groups can be used singularly or in combination.

A method of preparing a polyoctatriazacane comprising divalent bridginggroups comprises forming a mixture comprising i) a monomer comprisingtwo or more primary aromatic amine groups, ii) an optional diluentmonomer comprising one aromatic primary amine group, iii) an aldehyde,and iv) a solvent. The mixture is stirred while formic acid is added.Any aldehyde may be used, such as formaldehyde, paraformaldehyde,acetaldehyde, benzaldehyde, or the like. The equivalence ratio ofaldehyde to total moles of primary aromatic amine groups (e.g., diaminemonomer plus optional monoamine monomer) is preferably about 1:1 toabout 1.25:1. Formic acid is generally added in sub-stoichiometricquantities, such as less than 0.8 equivalents, between about 0.1equivalents and about 0.5 equivalents, for example about 0.5equivalents.

Non-limiting exemplary monomers comprising two primary aromatic aminegroups include 4,4′-methylenedianiline (MDA),4,4′-(9-fluorenylidene)dianiline (FDA), p-phenylene diamine (PD),1,5-diaminonaphthalene (15DAN), 1,4-diaminonaphthalene (14DAN), andbenzidene, which have the following structures:

Non-limiting exemplary diluent monomers includeN,N-dimethyl-p-phenylenediamine (DPD), p-methoxyaniline (MOA),p-(methylthio)aniline (MTA), N,N-dimethyl-1,5-diaminonaphthalene(15DMN), N,N-dimethyl-1,4-diaminonaphthalene (14DMN), andN,N-dimethylbenzidene (DMB), which have the following structures:

The diluent monomer can be used in an amount of 0 mole % to about 75mole % based on total moles of monomer and diluent monomer.

The solvent can be any suitable solvent. Preferred solvents includedipolar aprotic solvents such as, for example, N-methyl-2-pyrrolidone(NMP), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF),N,N-dimethylacetamide (DMA), Propylene carbonate (PC), and propyleneglycol methyl ether acetate (PGMEA).

A polyoctatriazacane as described herein may be coated onto a substrateby forming a first mixture comprising i) a monomer comprising twoaromatic primary amine groups, ii) an optional diluent monomercomprising one aromatic primary amine group, iii) an aldehyde, and iv) asolvent, coating the mixture on the substrate to form a precursor layer,and then distributing formic acid over the precursor layer to form apolyoctatriazacane coating. The substrate can be any structurally strongsubstrate, such as a semiconductor wafer (e.g., silicon wafer), mostmetals, refractory materials, and other polymers. Any suitable coatingtechnique (e.g., spin coating, dip coating, roll coating, spray coating,and the like) may be used. An adhesive bond may be formed in some casesif the first mixture is allowed to, or able to, penetrate into thesurface of the substrate before reacting with the formic acid.

In this context, a substrate may be, without limitation, an electronicdevice, microchip, microelectronic device, printed circuit board, harddisk drive platter, a portion of fluid filter, and portion of ahydrocarbon (e.g., petroleum, natural gas, or petro-chemical) processingfacility such as a pipe, pipeline, fluid pumping device, distillationcolumn, a reaction vessel, or storage tank.

The number average molecular weight (Mn) of a polyoctatriazacane can bein a range of 1000 to 100,000, preferably in a range of 1000 to 50,000,and most preferably in a range of 1000 to 20,000.

In one example, 0.050 g of p-phenylenedianiline (0.462 mmol, 1.0equivalents, purchased from Sigma-Aldrich Co., LLC, of St. Louis, Mo.and stored under nitrogen) and 0.0277 g paraformaldehyde (0.924 mmol,2.0 equivalents, washed with water, acetone, the diethyl ether, thendried over P₂O₅ prior to use) were combined in a dried vial with stirbarin a nitrogen-filled glovebox with 0.5 mL of dry DMSO (refluxed overCaH₂ for 96 hours prior and then distilled prior to use). Formic acid,0.004 g, was then added by syringe to the solution (0.231 mmol, 0.5equivalents). After 10 minutes, an aliquot of the resulting orangesolution was taken for ¹H-NMR analysis. FIG. 1 shows the resultingtrace, which is consistent with the following reaction scheme:

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

What is claimed is:
 1. A method, comprising: forming a reaction mixturecomprising a i) solvent, ii) an aldehyde, and iii) a monomer comprisingtwo primary aromatic amine groups; and forming a polyoctatriazacane byadding formic acid to the reaction mixture.
 2. The method of claim 1,wherein the solvent is selected from the group consisting ofN-methylpyrollidone (NMP), propylene carbonate (PC), dimethylacetamide(DMA), dimethylsulfoxide (DMSO), propylene glycol methyl ether acetate(PGMEA), dimethylformamide (DMF), and combinations thereof.
 3. Themethod of claim 1, wherein the monomer is selected from the groupconsisting of p-phenylenedianiline, 4,4′-methylenedianiline (MDA),p-phenylenediamine (PD), 4,4′-(9-fluorenylidenyl)dianiline (FDA), andcombinations thereof.
 4. The method of claim 1, wherein thepolyoctatriazacane comprises: a plurality of octatriazacane groupshaving the structure

 and a plurality of divalent bridging groups, each divalent bridginggroup comprising an aromatic group, wherein each divalent bridging groupis covalently bonded to an octatriazacane group at one of the starredbonds.
 5. The method of claim 4, wherein each divalent bridging grouphas the general structure

wherein R¹, R², R³, and R⁴ are each, individually, H, Cl, CN, F, NO₂,SO₃, imides, benzoxazoles, benzimidazoles, phenylquinoxalines,C_(x)H_(2x+1-y)R⁵ _(y), or C₆H_(5-a)R⁵ _(a), wherein R⁵ is Cl, F, SO₃,C₆H_(5-a)R⁶ _(a), or NH_(3-b)R⁶ _(b), wherein R⁶ is C_(x)H_(2x+1),C_(x)H_(2x), or C₆H₅, where in each instance x is an integer from 1 to4, y is an integer from 0 to 2x+1, a is an integer from 0 to 5, and b isan integer from 0 to 3; or the general structure

wherein L′ is a divalent linking group selected from the groupconsisting of *—SO₂—*, *—N(R′)—*, *—N(H)—*, *—CF₂—*, *—C(CF₃)₂)—*, —R″—,and combinations thereof, wherein R′ and R″ independently comprise atleast 1 carbon.
 6. The method of claim 5, wherein the divalent linkinggroup comprises fluorine.
 7. The method of claim 5, wherein L′ is ahydrocarbyl group having from 1 to 4 carbon atoms.
 8. The method ofclaim 5, wherein the aldehyde is formaldehyde or paraformaldehyde. 9.The method of claim 1, wherein the reaction mixture is coated onto asubstrate before adding the formic acid.
 10. The method of claim 4,wherein the polyoctatriazacane further comprises a plurality of diluentgroups having a structure selected from the group consisting of

wherein W′ is a monovalent radical selected from the group consisting of—N(R1)(R2), —OR3, and —SR4, wherein R1, R2, R3, and R4 are independentmonovalent radicals comprising at least 1 carbon, and wherein thestarred bond is linked to a nitrogen of an octatriazacane group.
 11. Themethod of claim 10, wherein the diluent group is: